CN103641243A

CN103641243A - Floating type light self-cleaning microorganism immobilization membrane for removing oil contamination polluting water and preparation method of membrane

Info

Publication number: CN103641243A
Application number: CN201310638067.3A
Authority: CN
Inventors: 潘超; 胡玉才
Original assignee: Dalian Ocean University
Current assignee: Dalian Ocean University
Priority date: 2013-12-03
Filing date: 2013-12-03
Publication date: 2014-03-19
Anticipated expiration: 2033-12-03
Also published as: CN103641243B

Abstract

The invention discloses a floating type light self-cleaning microorganism immobilization membrane for removing oil contamination polluting water and a preparation method of the membrane. Microorganisms are embedded into an inner layer of a porous polymer by using a coaxial electrostatic spinning technology to form a porous nanofiber membrane with a core-shell structure nanofiber, so that an oil absorbent felt floated on the water surface is formed, thus full contact between the microorganisms and greasy dirt is facilitated, the mass transfer resistance of the microorganisms and the greasy dirt is reduced and the catalytic activity of petroleum degradation microorganisms is effectively improved; a nanometer photocatalyst having the photocatalytic effect is immobilized on the surface of the core-shell structure nanofiber surface, so that the greasy dirty remaining on the surface of the fiber is decomposed under the action of the solar energy; moreover, the floating type light self-cleaning microorganism immobilization membrane has a light self-cleaning function, so that the repeating utilization rate of the oil absorbent felt is increased, and the greasy contamination treatment cost of the water is reduced.

Description

Removal water body is the immobilized film of the self-cleaning microorganism of floated light and preparation method for greasy dirt

Technical field

The present invention relates to the immobilized film of microorganism and preparation method for a kind of removal water body greasy dirt, especially the dirty absorption of oil-collecting, microorganism catalysis and photocatalysis technology be in an one, can reduce the resistance to mass transfer of microorganism and greasy dirt, the catalytic activity that effectively improves oil degradation microorganism and greasy dirt clearance and have the immobilized film of the self-cleaning microorganism of floated light and the preparation method for removal water body greasy dirt of light self cleaning function.

Background technology

At present, the treatment process for water body greasy dirt has Physical, biological process and photocatalytic method etc.

Physical is to adopt asphalt felt to adsorb swimming in the greasy dirt of the water surface, but existing asphalt felt adsorptive power is not strong, and oil suction aftertreatment is more loaded down with trivial details, recycles number of times low, has strengthened greasy dirt processing cost.

Biological process is to utilize high efficient petroleum degrading bacteria, as Rhodopseudomonas (Pseudomonas), Vibrio (Vibrio), acinetobacter (Acinetobacter), Flavobacterium (Flavobacterium), achromobacter (Achromobacter), Alkaligenes (Alcaligenes), enterobacteriaceae (Enterobacteriaceae), Corynebacterium (Coryhebacterium), the catalytic treatment water body greasy dirts such as genus arthrobacter (Arthrobacter) or bacillus (Bacillus), there is non-secondary pollution, efficiently, the advantages such as environmental protection, become the focus of current water treatment research.Biological process was that bacterium liquid is splashed on the open water surface in the past, but the open water surface is due to effects such as stormy waves, trends, the nutrition of microorganism or interpolation is easily diluted or washes away, therefore be difficult to nutrition, microorganism and oily close contact and it is remained in certain concentration range, implementing more difficult.For this reason, existing biological process is to adopt immobilized microorganism technique, in the region that soon highly effective petroleum degrading microorganism will be positioned to limit, as bacterium is fixed on stalk, or bacterium is combined with macro, effectively overcome free microorganism easy problem such as losss in water body oil spill biological restoration process, improve the ability that microorganism adapts to water body complex environment, and then raising oil spilling repairing effect.But existing immobilized microorganism technique can not be reused, still exist the problem that cost is high.

Photocatalytic method is in recent years emerging water body greasy dirt treatment technology, to utilize sun power to make the energy, by UV-light, intensify by water molecules and cause the active oxygen that electronics produces OH radical, the reactivity of OH radical is very high, the organic substances such as greasy dirt that reach photocatalyst surface can be carried out to oxygenolysis, finally become harmless CO ₂and water.Without making with medicament and treating processes there is no secondary pollution.But the photocatalyst adopting in this technology is at present TiO _2,the nano-powders such as ZnO, NiO or CuO, very easily along with wave is dispersed in water body, cause reclaiming difficulty, and cost increases.

Summary of the invention

The present invention is in order to solve the existing the problems referred to above of prior art, provide the dirty absorption of a kind of oil-collecting, microorganism catalysis and photocatalysis technology in one, the catalytic activity oil-collecting dirt clearance that can reduce the resistance to mass transfer of microorganism and greasy dirt, effectively improves oil degradation microorganism has the immobilized film of the self-cleaning microorganism of floated light and the preparation method for removal water body greasy dirt of light self cleaning function.

Technical solution of the present invention is: the immobilized film of the self-cleaning microorganism of floated light for a kind of removal water body greasy dirt, by electrostatic spinning nano fiber, formed, it is characterized in that: described electrostatic spinning nano fiber is coaxial three-decker, is followed successively by from the inside to the outside microorganism layer, porous polymer layer and photocatalysis layer.

Remove as mentioned above a preparation method for the immobilized film of the self-cleaning microorganism of floated light for water body greasy dirt, it is characterized in that carrying out as follows:

A. high efficient petroleum degrading bacteria being belonged to active bacterium liquid, to join mass percent concentration be in 5% ~ 20% hydrophilic polymer solution, and the concentration of volume percent of bacterium liquid is 0.01 ~ 0.5%, and concussion shakes up to bacterium liquid dispersed;

B. lipophilicity polymkeric substance is dissolved in organic solvent, compound concentration is that mass percent concentration is 5 ~ 30% solution, and room temperature lower magnetic force stirs 1 ~ 2h;

C. the solution of a, b step is recorded respectively in two shower nozzle coaxial electrically spun devices, take a step gained solution as kernel, b step gained solution are as outer, high-voltage power supply positive and negative electrode connects respectively stainless steel shower nozzle and aluminium foil, stainless steel shower nozzle is 5-30 cm to the distance of cylinder, injection electric is 3-30 KV, cylinder revolution is 300-2000 rpm/min, and fltting speed is 0.1-5 ml/h, obtains the poromeric coaxial core-shell nano tunica fibrosa of microorganism@;

D. resulting coaxial core-shell nano tunica fibrosa is dipped in to 0.5-2 h in the semi-conductor sol solutions with photocatalytic effect, semi-conductor nano particles static is assembled in fiber outside surface, forms the photocatalysis layer with light self-cleaning action.

Described hydrophilic polymer is polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone or polyacrylamide.

Described lipophilicity polymer poly propylene, polystyrene, polymethyl methacrylate, polyvinylidene difluoride (PVDF) or polymethyl siloxane.

Described organic solvent is dimethyl formamide, tetrahydrofuran (THF), N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).

The present invention utilizes coaxial electrostatic spinning technology, microorganism is embedded in to poromeric internal layer, form the porous nanofiber membrane with nuclear shell structure nano fiber, formation floats on the asphalt felt of the water surface, thereby promotion microorganism fully contacts with greasy dirt, the resistance to mass transfer that reduces microorganism and greasy dirt, effectively improves the catalytic activity of oil degradation microorganism; The nano-photocatalyst with photocatalytic effect is fixed on to nuclear shell structure nano fiber surface, can under the effect of sun power, the greasy dirt that residues in fiber surface be decomposed, there is light self cleaning function, thereby improved repeating utilization factor, the reduction water body Pollution cost of asphalt felt.The dirty absorption of oil-collecting of the present invention, microorganism catalysis and photocatalysis technology be in one, have applied widely, processing efficiency is high, cost is low, recovery utilization rate advantages of higher.

Accompanying drawing explanation

Fig. 1 is the structural representation of embodiment of the present invention nanofiber.

Fig. 2 is the scanning electron microscope diagram of electrospinning polyvinylidene fluoride nanometer tunica fibrosa (PVDF:10%).

Fig. 3 is the scanning electron microscope diagram of the coaxial nuclear shell structure nano tunica fibrosa of Alkaliphilic bacillus (Bacillus alcalophilus) bacterial strain SG@polyvinylidene difluoride (PVDF).

Fig. 4 is the embodiment of the present invention 1 Alkaliphilic bacillus (Bacillus alcalophilus) bacterial strain SG@polyvinylidene difluoride (PVDF)-TiO ₂composite nano fiber scanning electron microscope diagram.

Fig. 5 embodiment of the present invention 1 Alkaliphilic bacillus (Bacillus alcalophilus) bacterial strain SG@polyvinylidene difluoride (PVDF)-TiO ₂composite nano fiber is processed contaminated by diesel oil design sketch in water body.

Embodiment

Embodiment 1:

A. 1.0 g polyvinylpyrrolidone particles are distributed in 4.0 ml deionized waters, it is 20% polyvinylpyrrolidonesolution solution to dissolving completely, obtaining mass percent concentration that room temperature lower magnetic force stirs 2 h; 1 ml Alkaliphilic bacillus (Bacillus alcalophilus) bacterial strain SG bacterium liquid is joined in 12 ml polyvinylpyrrolidonesolution solution, concussion shakes up to dispersed, obtains SG-polyvinylpyrrolidone mixing solutions again;

B. by 1.0 g polyvinylidene difluoride (PVDF) grain dissolutions in 9 ml N-Methyl pyrrolidone solvents, room temperature lower magnetic force stirs 2 h, forms the sol solutions of homogeneous, stable, thickness;

C. the solution of a, b step is recorded respectively in two shower nozzle coaxial electrically spun devices, take a step gained solution as kernel, b step gained solution are as outer, high-voltage power supply positive and negative electrode connects respectively stainless steel shower nozzle and aluminium foil, stainless steel shower nozzle is 10 cm to the distance of cylinder, injection electric is 15 KV, cylinder revolution is 300 rpm/min, and fltting speed is 0.5 ml/h, obtains the coaxial core-shell nano tunica fibrosa of SG@polyvinylidene difluoride (PVDF);

D. resulting coaxial core-shell nano tunica fibrosa is dipped in to the TiO with photocatalytic effect ₂in sol solutions, after static absorption 30 min, take out and repeatedly rinse out superfluous TiO with distilled water ₂colloidal sol, obtains immobilization SG@porous polyvinylidene difluoride (PVDF)-TiO as shown in Figure 1 ₂coaxial nuclear shell structure nano tunica fibrosa finished product, 1:SG, 2: porous polyvinylidene difluoride (PVDF), 3:TiO ₂.

Fig. 2 is polyvinylidene fluoride nanometer fiber scanning electron microscope diagram, and as can be seen from Figure 2 styroflex diameter is in 1000 about nm, and it is more even to distribute, and surface is vesicular structure.Fig. 3 is the fiber SEM figure after the embodiment of the present invention 1 polyvinylidene fluoride nanometer fiber embedding SG, and fiber surface has a large amount of coarse pleated structures.Fig. 4 is embodiment of the present invention 1SG@porous polyvinylidene difluoride (PVDF)-TiO ₂coaxial nuclear shell structure nano tunica fibrosa, as can be seen from the figure fiber surface has a large amount of TiO ₂nano particle.Fig. 5 is SG@polyvinylidene difluoride (PVDF)-TiO ₂composite nano fiber catalytic film is processed contaminated by diesel oil design sketch in water body, and in 30 min, Diesel degradation rate reaches 93.65%.

Embodiment 2:

A. 1.0 g granule of polyvinyl alcohol are distributed in 9 ml deionized waters, room temperature lower magnetic force stirs 1 h to abundant swelling, and temperature rises to 70 ℃, continues to be stirred to solution clear, obtains concentration and be 10% polyvinyl alcohol solution; 0.5 ml Flavobacterium (Flavobacterium sp) bacterium liquid is joined in the polyvinyl alcohol solution that 10 ml prepare, concussion shakes up to dispersed again;

B. 1.0 g granules of polystyrene are dissolved in 3.5 ml tetrahydrofuran solvents, room temperature lower magnetic force stirs 1 h

Form the sol solutions of homogeneous, stable, thickness;

C. the solution of a, b step is recorded respectively in two shower nozzle coaxial electrically spun devices, take a step gained solution as kernel, b step gained solution are as outer, high-voltage power supply positive and negative electrode connects respectively stainless steel shower nozzle and aluminium foil, stainless steel shower nozzle is 10 cm to the distance of cylinder, injection electric is 10 KV, cylinder revolution is 500 rpm/min, and fltting speed is 1 ml/h, obtains the coaxial nuclear shell structure nano tunica fibrosa of Flavobacterium@expanded polystyrene;

D. resulting coaxial core-shell nano tunica fibrosa is dipped in to the TiO with photocatalytic effect ₂in sol solutions, after static absorption 30 min, take out and repeatedly rinse out superfluous TiO with distilled water ₂colloidal sol, obtains immobilization Flavobacterium@expanded polystyrene-TiO as shown in Figure 1 ₂coaxial nuclear shell structure nano tunica fibrosa finished product, 1: Flavobacterium, 2: expanded polystyrene, 3: TiO ₂.

Embodiment 2 gained tunica fibrosas have the performance of machine oil in good removal water body, at the degradation efficiency of 50 min inner engine oils up to 92.42%.

Claims

1. remove water body immobilized film of the self-cleaning microorganism of floated light for greasy dirt for one kind, by electrostatic spinning nano fiber, formed, it is characterized in that: described electrostatic spinning nano fiber is coaxial three-decker, be followed successively by from the inside to the outside microorganism layer (1), porous polymer layer (2) and photocatalysis layer (3).

2. remove as claimed in claim 1 a preparation method for the immobilized film of the self-cleaning microorganism of floated light for water body greasy dirt, it is characterized in that carrying out as follows:

A. it is in 5% ~ 20% hydrophilic polymer solution that active bacterium liquid high efficient petroleum degrading bacteria being belonged to joins mass percent concentration, and the concentration of volume percent of bacterium liquid is 0.01 ~ 0.5%, and concussion shakes up to bacterium liquid dispersed;